Photographic developer composition



Patented Sept. 7, 1954 PHOTOGRAPHIC DEVELOPER COMPOSITION George A.Reynolds, Rochester, N. Y., assignor to Eastman Kodak Company,Rochester, N. Y., a corporation of New Jersey No Drawing. ApplicationAugust 3, 1953, Serial No. 372,166

19 Claims. 1

R-CHg(CHOH)n-1-CHO=C =NH OH OH wherein R represents a hydroxyl groupwhen n represents a positive integer from 1 to 4 and R. represents ahydrogen atom when n represents a positive integer from 2 to 4.

The following compounds are representative of compounds having the abovegeneral formula with which my invention is concerned.

CHzOH imino-l-erythoascorbic acid HN=C noc': 1 ll H 0 OJ H9; H0 (3H JHzO H imino-l-ascorbic acid C=NH O i OH O H La O OH C H2OHimino-d-glucoascorbic acid HN=C HO (J HO ('3 0 EU H O Himino-G-desoxy-l-ascorbic acid HN=C HO H HO C 0 Hal HO 43H H O OHimino-l-rhamnoascorbic acid HN=C H O 0 Hot 0 H O C Himino-l-fucoascorbic acid HO [I H0 ((Ej HO JH H O H In) OHimino-d-glucoheptoascorbic acid Other compounds contemplated by theinvention which have the above general structure are imino-d-ascorbicacid, imino-l-ascorbic acid, imino-isoascorbic acid and otheriminoascorbic acid analogs, e. g., imino-sorboascorbic acid,imino-w-lactoascorbic acid, imino-maltoascorbic acid,imino-l-araboascorbic acid, imino-d-glucoascorbic acid,imino-d-galactoascorbic acid, imino-l-guloascorbic acid, andimino-l-alloascorbic acid.

As will be apparent, the above compounds difier principally in thestructure of the terminal group R-CH2-(CHOH)n iand in some cases thecompounds are stereoisomers. The compounds are described in particularby Pigman and Wolfrom, Advances in Carbohydrate Chemistry, AcademicPress, New York, 1946, pp. 80-82. Accordingly, the above iminoascorbicacid analogs are named to denote the particular sugar from which theycan be synthesized. It will be observed that the compounds arenon-aromatic and contain the characteristic mononuclear heterocyclicene-diol group. The compounds are particularly distinguished fromaromatic silver halide developing agents such as catechol or pyro gallolwhich show serious disadvantages such as strong tendency to form coloredoxidation products in the development reaction or on contact with theoxygen in the air which products discolor solutions and stainphotographic materials.

I have discovered that the developing rate of developer solutionscontaining the above enediol compounds can be markedly accelerated bythe addition to the ene-diol silver halide developing compositions of3-pyrazolidone compounds which themselves are only moderately activedeveloping agents for silver halide. The activity of the resultingdeveloper solution containing both the ene-diol and the pyrazolidone isvery much greater than would be expected from summing up the separateactivities. An added feature of the ene-diol-pyrazolidone developercompositions resides in the stability of the developing solution. Thatis, 3-pyrazolidone compounds such as 1-phenyl-3-pyrazolidone, are highlyunstable in alkaline developer compositions free of a preservative andtend to darken and lose development activity quickly particularlythrough aerial oxidation. On the other hand, when development is carriedout with the 3-pyrazolidone compounds in the presence of the enediolcompounds, the latter function as preservatives and the developer ishighly resistant to discoloration and loss of activity. Anotheradvantageous characteristic of the ene-diol-pyrazolidone developercompositions is that the developers show little tendency for theformation of silver sludge or for the formation of dichroic stain onsilver images. A further advantage is that since the ene-diol compoundsare very effective preservatives for the pyrazolidone developing agentsand are highly soluble in water, it

is possible to prepare concentrated develop-er or groups such as alkylpreferably of 1 to 4 carcompositions more readily than in the case wherea less soluble preservative such as sodium sulfite is used. A furthercharacteristic of the ene-diolpyrazolidone developer compositions of theinvention resides in the fact that the compositions behave as strongsurface latent image developers as opposed to internal latent imagedevelopers, as long as they are free of silver halide solvents such assodium sulfite. That is, developer compositions containing3-pyrazolidone compounds have been described in the literature butinvariably they have been compounded so as to con tain a silver halidesolvent such as sodium sulfite as a preservative. In order to convertsuch a developer composition to a surface latent image developer, I havefound it to be necessary to dispense with the silver halide solvent inthe developer composition. However, as mentioned, the 3-pyrazolidonedevelopers free of preservative are very unstable. When, according to myinvention, the ene-diol compounds are incorporated into the3-pyrazolidone developer compositions, the ene-diol compounds supply therequired preservative effect and the surface latent image developercharacteristics are maintained. Therefore, the fortuitous choice of3-pyrazolidone compounds to accelerate the development rate of theene-diol compounds has resulted in the latter compounds exerting acomplementary preservative effect as well as providing a stable3-pyrazolidone developer system which has surface latent imagedevelopment characteristics and shows no tendency for physicaldevelopment. For these reasons the developers of the invention are veryuseful in color development processes where a black-and-white developeris required.

An additional unexpected feature of the developers containing the3-pyrazolidone and ascorbic acid compounds resides in the fact thatsimilar developer compositions can be prepared, in which thepyrazolidone is replaced by a conventional developing agent, forexample, containing a mixture of N-methyl-p-aminophenol and ascorbicacid, which compositions do not exhibit the mentioned developmentacceleration effect to any great extent.

The 3-pyrazolidone developer compositions of the invention containingthe above ene-diol compounds can be readily converted to internal latentimage developer compositions by merely adding a silver halide solventsuch as sodium thiosulfate thereto. The resultant internal latent imagedeveloper composition, by virtue of the presence of one of the mentionedene-diol compounds, likewise possesses excellent keeping properties evenin the absence of the usual sulfite preservative.

The 3-pyrazolidone silver halide developing agents employed in thedeveloper compositions together with ascorbic acid and its analogs, havethe general formula in which the R groups each represent varioussubstituents such as hydrogen, alkyl or aryl groups, for example, R1 canbe hydrogen or a group such as alkyl preferably containing from 1 to 4carbon atoms, or an aryl group of the benzene or naphthalene seriessubstituted or not, and R2, R3, R4 and R5 can be hydrogen atoms,

bon atoms or aryl such as phenyl.

The following compounds are representative of 3-pyrazolid0ne silverhalide developing agents which are useful in the developer compositionsof the invention:

cocoacncnyswrog- 14. 1-phenyl-4,4-dimethyl-3-pyrazo1idone 15. 1 maminophenyl 4 methyl 4 propyl- S-pyrazolidone 16. 1 o chlorophenyl 4methyl 4 ethyl- S-pyrazolidone 17. 1 m acetamidophenyl 4,4 diethyl 3-pyrazolidone 18. 1 (p 3 hydroxyethylphenyl) 4,4 dimethyl-3-pyrazolidone19. 1 p hydroxyphenyl 4,4 dimethyl 3- pyrazolidone 2'0. 1 pmethoxyphenyl 4,4 diethyl 3- pyrazolidone 21.1-p-tolyl-4,4-dimethyl-3-pyrazolidone 22. 1 (7 hydroxy 2 naphthyl) 4methyl- 4-n-propy1-3-pyrazolidone 23.1-p-diphenyl-4,4-dimethyl-3pyrazolidone 24. 1- (p-p-hydroxyethylphenyl)-3-pyrazolidone 25. 1-o-tolyl-3-pyrazolidone 26.1o-tolyl-4,4-dimethyl-3-pyrazolidone The 4,4-dialkyl-3-pyrazolidonecompounds 13 to 23 and 26 above are particularly efiicacious for use inthe developer compositions of my invention inasmuch as they are moreactive developing agents than are compounds 1 to 12 which contain asingle substituent or only hydrogen atoms in the 4-position of thepyrazolidone nucleus. The 4,4-dialkyl-3-pyrazolidone compounds aredescribed and claimed in the Allen et al. U. S. patent applicationSerial No. 372,148 filed concurrently herewith. Thew-hydroxyalkyl-3-pyrazolidones, for example, compounds iminoreductonederivative such as p-aminobenzoic acid reductone, mand p-aminosalicylicacid reductone and sulfanilic acid reductone are similar in structure tothe imino ascorbic acid compounds and their use in developercompositions is disclosed and claimed in the Henn and Reynolds U. S.patent application Serial No. 372,168 filed concurrently herewith.

Example 1 The striking superadditivity obtained by combining thepyrazolidones and ene-diols, is shown in the following table. It is seenthat the individual agents develop only weakly, but that when combined,they develop vigorously, producing images of high density.

These formulas all contained 25 grams of sodium sulfite and 25 grams ofmonohydrated sodium carbonate per liter, in addition to the indicateddeveloping agents. In each case the pH of the formula was adjusted to10.0 with acetic acid, to bring all solutions under parallel conditions.

The formulas compare the activity of the enediol ascorbic acid alone atan 0.02 molar concentration (3.5 grams per liter), of the pyrazolidoneby itself, at 0.0025 molar concentration (0.4 to 0.5 gram per liter),and combinations of the agents in these concentrations. The activity wastested with a fine grain positive film, given a step wedge exposure anddeveloped for a series of times at 68 F. and with high agitation.

18 and 24 above, are also especially useful in concentrated formulas, inreplenishers and in the presence of high salt concentrations where theirincreased solubility enables obtaining and holding adequate amounts ofthe pyrazolidone compound in solution. The compounds are described andclaimed in the Allent et a1. U. S. patent application Serial No. 372,148filed concurrently herewith and the Reynolds and Tinker U. S. patentapplication Serial No. 372,167 filed concurrently.

The ene-diol compounds imino-d-glucoascorbic acid above obtained fromd-glucose (J. Chem. Soc. 1934, p. 1194) is representative of a number ofene-diol compounds containing the iminoascorbic acid group derived fromsugars. The compound is of particular value in my invention since itsdevelopment rate is markedly accelerated by the 3-pyrazolidone silverhalide developing agents, particularly l-phenyl-3-pyrazolidone. Theother ene-diol compounds containing the imino group can be prepared bythe methods of the reference immediately above from, for example,erythrose, galla-ctose, sorbose, mannose, maltose, and lactose and arelikewise useful in the 3-pyrazolidone developer compositions where thelatter compounds appreciably accelerate the development rate of theene-diol compounds.

As will be apparent above, the

Example 2 The following developer compositions are particularly suitableas negative developers for color films:

(1) Without sulfite: Grams/liter Sodium hexametaphosphate 0.5 Potassiumbromide 1.0 Sodium carbonate monohydrate 25.0 Potassium iodide 0.002l-phenyl-3-pyrazolidone 1.0 Imino-d-glucoascorbic acid 12.51-phenyl-5-mercapto tetrazole 0.01 Water to make 1.0 liter (2) Withsulfite: Grams/liter Sodium hexametaphosphate 0.5 Sodium sulfite 40.0Sodium carbonate monohydrate 25.0 Potassium bromide 1.0 Potassium iodide0.002 l-phenyl-3-pyrazolidone 1.0 Imino-d-glucoascorbic acid 12.1-phenyl-5-mercapto tetrazole 0.01

Water to make 1.0 liter The developers of this example can be used inany of the well-known processes of color development Where ablack-and-white developer is required. The developers are especiallyuseful in 7 mixed grain color processes employing films such asdisclosed in Mannes et a1. U. S. Patent 2,388,856 or in the Carroll eta1. U. S. Patent 2,614,925, October 21, 1952, wherein, for example, isshown a two-layer film, one layer containing blue-sensitive silverhalide, the other containin a mixture of green and red-sensitive silverhalide grains. When the developers immediately above are used in thecolor process of the patents as the negative developer for such a filmit is observed, particularly with the Formula 1 free of sulfite, thatphysical development effects are minimized with the result that cleanhighlights free of stain are obtained and the color developed imageshave increased saturation because of decreased physical development inthe negative developer of the invention.

Results similar to those of the above examples are obtained whendeveloper compositions, containing or free of silver halide solvents,are prepared from mixtures of at least one of the indicated3-pyrazolidone compounds and at least one of the iminoascorbic acidcompounds. The enediol-pyrazolidone developer composition of the aboveexample exhibits internal latent image development characteristicsparticularly by virtue of the presence of the silver halide solvent.Particularly valuable developer compositions in addition to thatexemplified above, are those containing imino-d-glucoascorbic acid andeither l-phenyl-B-pyrazolidone or a l-tolyl-3-pyrazolidone such asl-p-tolyl-3-pyrazolidone or l-ptolyl-4A-dimethyl-3-p-yrazolidone or al-(p-flhydroxyalkylphenyl) 4,4 dialkyl 3 pyrazolidone such as1-(p-c-hydroxyethylphenyl)- 4,4-dimethyl-3pyrazolidone, or a1-(p-B-w-hY- droxyalkylphenyl) -3-pyrazolidone' such as 1-(pfl-hydroxyethylphenyl) -3-pyrazolidone.

It will be understood that my invention as specified by the claimshereinafter, includes the mentioned developer compositions in either theliquid form exemplified above, or in the dry powder form as packageddeveloper formulas suitable for dissolving in water to form a liquiddeveloper. Such dry compositions include the mentioned 3-pyrazolidonecompounds, the ene-diol compound, and alkaline material such as sodiumcarbonate, caustic alkali or sodium metaborate.

What I claim is:

1. A photographic developer composition comprising an alkaline material,a 3-pyrazolidone silver halide developing agent and a compound havin thegeneral structure RCH2(OHOH),.-1CHC:CC=NH wherein R represents ahydroxyl group when n represents a positive integer from 1 to 4 and Rrepresents a hydrogen atom when n represents a positive integer from 2to 4.

2. A photographic developer composition comprising an aqueous alkalinesolution containing a mixture of a 3-pyrazolidone silver halidedeveloping agent and a compound having the general structure prising anaqueous alkaline solution containing a mixture of a 3-pyrazolidonesilver halide developing agent and a compound having the struc- 4. Aphotographic developer composition comprising an aqueous alkalinesolution containin a mixture of a 3-pyrazolidone silver halidedeveloping agent and a compound having the structure 5. A photographicdeveloper composition comprising an aqueous alkaline solution containinga mixture of a 3-pyrazolidone silver halide developing agent and acompound having the structure 6. A photographic developer compositioncomprising an aqueous alkaline solution containing a mixture of aB-pyrazolidone silver halide developing agent and a compound having thestructure 7. A photographic developer composition comprising an aqueousalkaline solution containing a mixture of a 3-pyrazolidone silver halidedeveloping agent and imino-d-glucoascorbic acid.

8. The developer composition of claim 2 wherein the designated3-pyrazolidone is 1-phenyl3- pyrazolidone.

9. The developer composition of claim 2 wherein the designatedB-pyrazolidone is a 4,4-dialkyl- 3-pyrazolidone.

10. A photographic developer composition comprising an aqueous alkalinesolution containing a mixture of a 1-tolyl-3-pyrazolidone andiminod-glucoascorbic acid.

11. A photographic developer composition comprising an aqueous alkalinesolution containing a mixture of 1-p-tolyl-4,4-dimethyl-3-pyrazolidoneand imino-d-glucoascorbic acid.

12. A photographic developer composition comprising an aqueous alkalinesolution containing a mixture of 1-phenyl-4A-dimethyl-3-pyrazolidoneand. imino-d-glucoascorbic acid.

13. A photographic developer composition comprising an aqueous alkalinesolution containing a mixture of1-(p-/3-hydroxyethy1phenyl-3-pyrazolidone and imino-d-glucoascorbicacid.

14. A photographic developer composition comprising an aqueous alkalinesolution containing a mixture of 1-(p-B-hydroxyethylphenyl)-4,4-dimethyl3 pyrazolidone and imino d glucoascorbic acid.

15. A photographic developer composition comprising an aqueous alkalinesolution containing a mixture of 1-phenyl-3-pyrazolidone andiminod-glucoascorbic acid.

16. A photographic developer composition comprising an aqueous alkalinesolution containing a mixture of 1-p-tolyl-3-pyrazolidone andiminod-glucoascorbic acid.

17. A photographic developer composition comprising an aqueous alkalinesolution containing a mixture of a 3-pyrazolidone silver halidedeveloping agent and a compound of the class consisting ofimino-l-ascorbic acid, imino-d-ascorbic acid, imino-l-erythroascorbicacid, imino-l-glucoascorbic acid, imino-d-glucoascorbic acid, iminodgelactoascorbic acid, imino l guloascorbic acid, imino-l-alloascorbicacid, imino-d-glucoheptoascorbic acid, imino 1 rhamnoascorbic acid,imino-l-fucoascorbic acid, imino-l-araboascorbic acid,imino-sorboascorbic acid, iminoisoascorbic acid,imino-fi-desoxy-l-ascorbie acid,

10 imino-w-lactoascorbic acid and imino-maltoascorbic acid.

18. The developer composition designated in claim 1 which has beenadapted to the development of the internal latent image of exposedsilver halide by the addition of a silver halide solvent.

19. The developer composition designated in claim 1 which is free of asilver halide solvent.

No references cited.

1. A PHOTOGRAPHIC DEVELOPER COMPOSITION COMPRISING AN ALKALINE MATERIAL,A 3-PYRAZOLIDONE SILVER HALIDE DEVELOPING AGENT AND A COMPOUND HAVINGTHE GENERAL STRUCTURE